Molded hats having improved shape retention and recoverability

ABSTRACT

A molded hat having improved shape retention and recoverability properties wherein the fabric of the crown and brim comprises a single unit eliminating the need for sewing the brim to the crown, said fabric containing a stabilizing polymeric composition. These molded hats are prepared by placing the stabilized fabric in a hat mold and thereafter applying heat and pressure to effect the desired shape. The improved shape retention and recoverability properties result from the presence of the polymeric composition in the fabric.

O United States Patent 1151 3,673,611 Cain et al. [451 July 4, 1972 [54] MOLDED HATS HAVING IMPROVED [56] References Cited SHAPE RETENTION AND UNITED STATES PATENTS RECOVERABILITY 1,682,870 9/1928 Van Husen ..2/194 [72] Inven o Jam P- p g; J n 2,112,384 3/1938 Sloan et al. ..2/ 175 Cross, Anderson, both of SC. 2,495,640 1/1950 Musicat 2/194 UX 3,156,924 11/1964 Hoffman et al. ..2/194 [73] Assgnee' ggggfi x g Research 3,317,645 5/1967 Nirenberg ..264/258 3,385,653 5/1968 Whitfield et a1. ..8/1 15.5 [22] Filed: May 18, 1970 Primary Examiner-Robert F. Burnett Appl' 37464 Assistant Examiner-Raymond O. Linker, .lr.

Related Us Applicau-on Data Attorney-Norman C. Armitage and H. William Petry [63] Continuation of Ser. No. 624,511, March 20, 1967, [57] ABSTRACT abandoned.

A molded hat having 1mproved shape retent1on and recovera- 52 11.5.0 ..2/192, 8/128, 161/89, bility Propeflies wherein the fabric of the Crown and brim 161/98 223/12 264/258 264/324 comprises a single unit eliminating the need for sewing the 51 1111.01. ..A42b 1/00, A421: 1 /00, D06m 3/00 brim to the crown, Said fabric containing a Stabilizing [58] Field of Search ..161/82, 88, 89,98, 170; Polymeric composition These molded hats are Prepared by 264/257, 258, 324; 2/175, 192, 194; 8/128, 127.6; placing the stabilized fabric in a hat mold and thereafter ap- 223/12 plying heat and pressure to effect the desired shape. The improved shape retention and recoverability properties result from the presence of the polymeric composition in the fabric.

3 Claims, 4 Drawing Figures PATENTEDJUL 4 m2 357361 1 sum 10F 2 INVEHTORS l JAMES P. CAIN Y JOHN H. CROSS ATTORNEY PATENTEDJUL' 41m 3. 673,61 1

' sum 2 or 2 2.. JOHN H.CROSS ATTORNEY MOLDED HATS HAVING IMPROVED SHAPE RETENTION AND RECOVERABILITY This application is a continuation of Application Ser. No. 624,51 1, filed Mar. 20, 1967, now abandoned.

BACKGROUND OF THE INVENTION This invention relates to shaped articles of wearing apparel, and more particularly, to the manufacture of molded hats wherein the crown and brim comprises a single unit.

The manufacture of wearing apparel and other textile articles by the molding or shaping of textile fabrics has been an attractive goal for many years. Most articles of the nature, for example, hats, brassiere cups, shoe uppers, gloves, raincoats, etc., have been prepared from a, relatively large number of pieces of material which are cut to the desired shape and stitched together. For example, the crown of a hat can comprise from four to eight separate pieces cut in a particular shape and secured together. The brim of a hat is made of one or more additional strips of fabric cut to the shape and secured to the lower edge of the crown. These types of hats do not present the smart pleasing appearance of hats which are made of one piece. One reason, among others, for this lack of smart appearance is that these hats have a number of unsightly seams running up the crown. Furthermore, hats prepared in this manner do not usually possess the desired degree of shape retention and resilience, and must, therefore, be reblocked and reshaped periodically to restore the hats to their original shape. Needless to say, such operations are costly and time consuming. Attempts to improve the shape retention of such hats and other shaped articles by utilizing linings of rubber, paper and other materials which can impart a desired degree of stiffness to the article have been somewhat successful. Attempts have also been made to treat or spray the fabrics, generally after the article has been formed, with a liquid such as shellac or enamel to improve the shape retention properties of the articles. However, articles treated in this manner are necessarily very stiff and do not have the desirable amount of resiliency.

' The use of thermoplastic fabrics for the manufacture of wearing apparel and other articles has been somewhat successful although such a method is not too desirable wherethe finished article must be flexible and possess a smooth hand. The preparation of such articles from thermoplastic fabrics is generally accomplished by the application of heat to the thermoplastic material while permitting deformation or stretching into thedesired shape. After formation is complete, the fabric is then set by an effective reduction of temperature. During the procedure, however, a greater degree of strain is exerted in certain fabric areas by the application of stress or tension sufficient to obtain the required displacement. For instance, in the manufacture of hats, there is a maximum amount of displacement found in the area of the crown of the hat as compared to the minimum fabric displacement required for the brim. The non-uniform application of stretching tension results in a finished product characterized by undesirable differences in fabric porosity and general appearance. Additionally, structural weaknesses within the shaped article are produced, and the desired flexibility is substantially diminished. Furthermore, molded articles of wearing apparel prepared exclusively from thermoplastic fabrics are generally stiff and inflexible as a result of the temperatures required during the shaping process.

Molded hats from fiat-needle felted fabrics having an intermediate thermoplastic shrinkable member therein have been prepared by needling batting materials on each side of the intermediate thermoplastic layer and then shrinking and molding the felted fabric to form the molded hats. The procedure described in [1.8. Pat. No. 3,156,926 involves preheating the needle-felted fabric, and while the thermoplastic layer is still warm and in a plastic state, molding the fabric in an unheated mold of the desired shape to cause the fabric to be stretched and molded to the desired shape.

Molded articles of wearing apparel also have been prepared from textile fabrics comprised of natural fibers in the form of discrete fiber assemblies, for example, woven or knitted woolen fabrics, by preparing a composition of the textile fabric and a layer of a fixed structure of a synthetic thermoplastic composition are described in co-pending Application Ser. No. 624,510, now abandoned.

The preparation of molded hats from composite fabrics comprising a layer of synthetic thermoplastic compositions and at least one layer of a textile fabric containing keratin fibers wherein the textile fabric is treated with a reducing agent and an aldehyde-generating compound prior to molding is described in co-pending Application Ser. No. 627,25l now US. Pat. No. 3,542,616 issued Nov. 24, l970. Although the molded articles of wearing apparel described in the co-pending applications exhibit an unusual degree of shape retention and resiliency, there remains a need for a method of preparing molded hats with the desired degree of stability and resistance to stress release and puckering without the use of fixed structures of thennoplastic resins which account for the substantial portion of the cost of the materials used to prepare molded hats. I-Ieretofore,'the use of such thermoplastic layers has been believed to be necessary to provide hats with the desired properties.

SUMMARY OF THE INVENTION and brim comprises a single unit, said fabric containing a stav bilizing polymeric composition and being resistant to shrinking and distortion.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view of a molded hat body immediately after coming out of the mold.

FIG. 2 is a front view of a machine for molding hats, partially sectioned, with the composite fabric in place.

FIG. 3 is an enlarged transverse sectional view of the outer crown and brim mold and the annular brim die showing the composite fabric held in position between the outer crown and brim mold and the annular brim die.

FIG. 4 is a view similar to FIG. 3 with the inner crown die lowered into the cavity of the outer crown mold and the com- .posite fabric between the inner crown die and the outer crown mold and between the inner brim die and the outer brim mold.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The molded hats of this invention generally are prepared by treating a textile fabric with a stabilizing polymeric composition, preparing a laminate (generally two-ply) from said treated fabric, and thereafter converting the laminate to the desired hat shape in a molding apparatus similar to the apparatus described in FIGS. 2-4. Hat shells also have been prepared from a single ply of treated fabric and from laminates composed of one layer of treated fabric and a layer of non-treated fabric. As can be seen, at least one layer of fabric must be treated with the stabilizing polymeric compositions of this invention prior to molding.

The fabrics which are useful in the preparation of the hats of this invention are textile fabrics containing at least some natural fibers such as cellulosic and protein fibers. Such fibers include cotton, flax, raime, wool, alpaca, vicuna, mohair, cashmere, guanaco, camel hair, llama, fur, leather, suede and silk. While the stabilizing polymeric compositions are particularly effective on fabrics composed essentially of natural fibers,

polyethylene terephthalate; and acrylic fibers such as of this invention include those obtained from discrete fiber assemblies such as yarns by weaving, knitting, or braiding, as well as felts or layers of fibers in batt form.

It has now been discovered that if the fabric is treated with a stabilizing polymeric composition and then molded into a hat having the desired shape, the resulting product exhibits improved shape retention and recoverability properties. For example, it is possible to manually deform -the hat by pressing down on the crown and by twisting the hat, and upon releasing the pressure or twisting force, the molded hat immediately returns to its original shape. Typical examples of such stabilizing treatments include additive type treatments wherein polymeric compounds are added to the textile fabric. Although it is preferred to use polymeric compounds which react with the natural fibers in the textile fabric, the stabilization of the fabricalso may be accomplished by simply coating the fibers with a non-reactive polymeric coating composition so as to provide the desired degree of stability and body to the fabric. Systems which have been found to be especially suitable for stabilizing the fabrics are interfacial polymerization systems such as those involving the formation of poly-(hexamethylene sebacate) through interfacial polymerization techniques, treatments with reactive copolymers and terpolymers based on the vinyl type monomers, treatments with polyepoxide-polyamine compositions, treatments with reactive and non-reactive polyurethanes, treatments with. reactive and non-reactive polyolefins, and treatments with emulsions of certain acrylic esters such as, for example, polymethylene methacrylate, polyethyl methacrylate, polypropyl methacrylate and polybutyl methacrylate.

Treatment of the fabrics with isocyanate reaction products produces fabrics which are especially useful in the preparation of themolded hats. Among the isocyanate reaction products which may be employed are isocyanate reaction products selected from the following general categories: urethanes prepared from a polyfunctional isocyanate and polymeric polyhydroxy compound; and the reaction products of a polyfunctional isocyanate and polymeric polyfunctional compoundssuch as polyesters, polyamides, polyepoxides, formaldehyde resins and polyepichlorohydrins. The isocyanate reaction products may be applied to the fabric as a solution in prepolymer form or in separate two-step applications forming the urethane on the fabric in situ.

Regardless of the system utilized, however, it is preferred that the ratio of isocyanate to active hydrogen compounds in the system be at least about 0.4 and most preferably greater than 1.0. By pre-polymer" as employed herein is meant the reaction products of polyfunctional isocyanate and the second polymeric compound carried to an extent below which a gel is formed which is insoluble in one of the organic solvents, and particularly the chlorinated hydrocarbons.

Among the suitable isocyanates that may be used in accordance with this invention are included aryl diisocyanates such as 2,4-tolylene diisocyanate, 4,4-diphenyl methane diisocyanate, 1,5-naphthylene diisocyanate, l-isopropyl benzene-3,5-diisocyanate and benzene-l,2,4-triisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; as well as mixtures thereof including the equivalent isothiocyanates.

Any of the above isocyanate-terminated compounds, either in pre-polymer or monomer form (as in the one-shot technique) may be blocked if desired, with phenol or any of the well-known blocking agents for isocyanates. The blocking group is activated byheat and removed to provide available isocyanate groups for reaction with the functional groups of the natural-fibers.

By polymeric polyhydroxy compound is meant a linear long-chain polymer having a terminal hydroxy group including branched, polyfunctional, polymeric hydroxy compounds as set forth below. Among the suitable polymeric polyhydroxy compounds, there are included polyether polyols such as the polyalkylene ether glycols, polyalkylene-aryleneetherthioether glycols and polyalkyleneether triols. Mixtures of these polyols may be used when desired.

The polyalkylene ether glycols may be represented by the formula HO(RO),,H, wherein R is an alkylene radical which need not necessarily be the same in each instance, and n is an integer. Examples of such glycols include polyethyleneether glycol and polypropyleneether glycol. The polyalkyleneether triols are prepared by reacting one or more alkylene oxides with one or more low molecular aliphatic triols. The alkylene oxides most commonly used have molecular weights between about 44 and 250, and these include, for example, ethylene oxide, propylene oxide,butylene oxide and 1,2-epoxy octane.

By polymeric polyfunctional compound is meant a longchain polymer containing at least two groups having at least one active hydrogen atom as determined by the Zerewitinoff method. Examples of such compounds include polyesters, polyamides, polyepoxides, formaldehyde resins polyepihalohydrins.

The polyesters generally are prepared by condensing an excess of a polymeric or monomeric polyhydroxy compound with a polyacid, or by esterifying a hydroxy substituted acid with a polyhydroxy compound. Among the suitable acids are the alkane dibasic acids, alkene dibasic acids and aryl dibasic acids. The polyols which are reacted with these acids to form polyesters have been discussed previously.

The polyepoxides which are reacted with polyisocyanates are organic compounds containing at least two epoxy groups per molecule and may be saturated or unsaturated, aliphatic, cycle-aliphatic, aromatic or heterocyclic and may be substituted with non-interfering groups such as hydroxy groups, other radicals etc. Polyepoxides containing ether groups may be prepared as well known in the art by reacting a polyol with a halogen-containing epoxide employing at least two moles of the epoxide per mole of polyol. Thus, for example, epichlorohydrin may be reacted without a polyhydric alcohol in an alkaline medium. In the other techniques the halogencontaining epoxide is reacted with a polyhydric alcohol in the presence of an acidic catalyst such as boron trifluoride,'and the product is then reacted with an alkaline compound to effect a dehydrohalogenation. Examples of such halogen-containing epoxides include epichlorohydrin, epibromohydrin and 3- chlorol,2-poxybutane. I

Polyepoxides which do not contain ether groups may be employed. However, the polyepoxides containing ether groups are preferred. More particularly, the polyepoxide polyethers of the class of glycidyl polyethers of polyhydric alcohols or polyhydric phenols are preferred. These compounds may be considered as being derived from a polyhydric alcohol or polyhydric phenol by etherification with at least two glycidyl groups having the structure Typical examples of such compounds include glycidyl polyethers of glycerol, glycol, or any of the other polyols listed previously as useful for reaction with halogen hydrogen containing epoxides. Mixtures of different polyepoxides are also contemplated as useful in the reaction with isocyanates.

The polyamides used in the reactions of the isocyanates are those derived from polyamines and polybasic acids by any of the methods known in the art. The polyamines include ethylene diamine, diethylene triamine and tetraethylene pentarnine. Typical polycarboxylic acids include glutaric acid, adipic acid, terephthalic acid and malonic acid. The polyamides may have molecular weights varying from about 1,000 to 10,000 and melting points from about 20 to 200 C.

As mentioned previously, the fabrics of this invention may be stabilized by treatment with polymeric polyepoxides per se or with a cured polyepoxide obtained by treating the fabric and I with a solution containing polyepoxide, preferably a polyether polyepoxide, and an amine catalyst and thereafter subjecting the treated fabric to an elevated temperature to cure the polyepoxide in the fibers of the fabric. Any of the polyepoxides and amine catalysts listed previously, as well as those known in the art, such as those disclosed in US. Pat. No. 2,829,071 may be used to stabilize the fabrics in accordance with the process of this invention.

Polyolefins which are useful for treating the fabrics used to prepare the molded hats of this invention include high molecular weight polyethylenes, polypropylenes, polybutenes and mixtures thereof as well as reactive derivatives thereof such as the chloro sulfonated polyethylenes, vinyl acetate, vinyl chloride, vinyl alcohol etc.

The incorporation of acid polymers into the fabric also provides molded hats with the desired properties. Acid polymers contemplated as being useful within the present invention are prepared from any of the polymerizable acids, i.e., those containing unsaturated groups. These polymers may be homopolymers of the acids or interpolymers of the acid and other monomers. Such acids include, for example, acrylic acid, maleic acid, methacrylic acid, polymerizable sulfonic acids and polymerizable phosphoric acids. Suitable monomers which may be copolymerized with the above acids include esters of the above acids such as ethylacrylate and methyl methacrylate; alkyl fumarates and maleates; vinyl halides such as vinyl chloride; and other vinyl monomers such as styrene, acrylonitrile and butadiene. Generally, the acid polymers and copolymers must contain at least percent by weight of the acid monomer.

The acid polymers, as a general rule, are emulsion polymers containing varying amounts of solids, normally in the range of about 25 to 50 weight percent. The polymer emulsion should be present in the pad bath or other application mediums in the range of about 2.5 to 40 weight percent.

Mixtures of the above-described monomers and polymers also may be applied to the fabrics of this invention to provide the desired properties. For example, terpolymers of ethylene, sodium methacrylate and methacrylic acid manufactured by E. I. du Pont de Nemours & Co. under the tradenarne Surlyn," and terpolymers of vinyl acetate, methacrylolyl chloride and ethylene available under the tradename Zeset from E. I. du Pont de Nemours & Co. are particularly useful. Mixtures of the above terpolymers with polymeric polyepoxides in the presence of an amine catalyst also provide the desired results.

The various polymeric compositions may be applied to the fabrics by conventional techniques such as by knife'coating, rolling, printing, dipping and spraying, although the polymeric coatings are generally applied with ordinary pad rolls. The compositions may be deposited as solutions, dispersions or emulsions as long as the solvent or liquid carrier is not reactive with polymeric compositions. Thus, aqueous or organic solvents may be utilized. Suitable organic solvents include halogenated hydrocarbons such as trichloroethylene, methylene chloride, perchloroethylene and chloroform; aromatic solvents such as toluene and benzene; and other solvents such as n-butyl acetate, dioxane, methyl isobutyl ketone and N,N-dimethyl formamide.

The polymeric stabilizing compositions or solutions thereof generally are applied to the fabric to provide from about 2 to about 50 percent or more, based on the weight of the fabric, of dry polymer. In some instances, it is possible to deposit greater amounts of polymer without affecting the desirable properties of the fabric. As a general rule, however, the use of large amounts of polymeric composition provides fabrics which are moldable but are characterized by undesirable stiffness. Thus, the fabric, depending upon its style and composition, preferably contains from about 2 to percent based on the weight of the fiber, of the polymeric stabilizing composition. The precise amounts can be readily determined by one skilled in the art taking into consideration the fabric, the polymeric composition and the desired properties.

The fabrics of this invention may berendered water repellent by application of any of the well known water-repellency treatments such as wax emulsions, silicones, organo-chromium compounds and the fluoro-chemicals. The fluorochemicals are a particularly useful class of water-repellents since these also offer some measure of oil-repellency to treated fabrics. The fluorochemicals used for water-repellency include compounds based on chromium complexes of perfluorocarboxylic acids, chromium complexes of perfluoralkylmonocarboxylic acids and fluorinated acrylic and methacrylic esters.

While fluorochernicals can be used alone to confer waterand oil-repellency to the fabrics, the results obtained can be considerably improved by the addition of other conventional water-repellents to the finishing bath. For example, Minnesota Mining and Manufacturing Companys Scotchgard process is based on a mixture containing about 0.6 percent of fluorochemical solids, l to 2 percent of a conventional durable water-repellent and from about 1 to about 1.5 percent of an arninoplast, e.g., melamine formaldehyde. The water-repellent mixtures are applied to the fabric by any of the well known methods such as padding, dipping, rolling, etc., squeezed, dried and baked at temperatures up to 200 C.

In most applications, it is preferred that more than one layer of the treated fabric be combined to form the molded hat. The use of laminates of two or more layers of fabric results in hats having superior shape retention and resilience although the use of excessive layers of fabric results in hats which are too heavy and bulky. The adhesive which is used to bond the various layers of textile fabric are preferably curable polymeric compositions which are non-tacky after curing. Elastomers which are soluble or dispersible in a liquid carrier are particularly useful as adhesives, and these include, for example, those elastomers prepared from acrylates, natural rubber, styrene butadiene, butadiene-acrylonitrile, butyl rubber, ethylene propylene rubber, chloro sulfonated polyethylene, fluorocarbon rubber, and urethane elastomers prepared from either polyesters or polyethers. Optimum resilience is achieved when the adhesive is natural rubber or a synthetic rubber such as the chloroprene rubbers. Where it is desired to produce a molded hat which is particularly resistant to chlorinated solvents and aging, cross-linked neoprene rubbers are used. The textile fabric layers may be bonded together by applying the adhesive to the fabric and thereafter pressing the layers together. The adhesive can be applied to the substrates as a continuous or discontinuous layer by conventional techniques such as knifecoating and pad rolls.

The amount of adhesive applied to the fabric is not critical although enough adhesive should be applied to provide a satisfactory bond between the layers of the laminate. Generally, from about 2.5 to about 25 percent by weight of adhesive, based on the weight of the fabric, is used.

Molded hats having particularly desirable properties are prepared from two-ply laminates wherein two layers of fabric are bonded together with an adhesive composition. Such twoply laminates allow the preparation of a one-piece molded hat which can be molded in one operation eliminating the need for sewing the brim of the hat to the crown. This embodiment also eliminates the need for subsequent application of a lining material. Furthermore, the two layers of fabric need not be identical. This is, where only one layer may be exposed or visible, the second layer, generally an inner layer, may be combined of less expensive fibers which have particularly aesthetic properties such as a pleasing hand. Examples of such inner layers include inexpensive cotton fabrics or smooth fabrics such as silk.

On the other hand, where both layers of the textile fabric will be visible, it is often desirable that both layers be comprised of the same textile fabric. For example, in molded hats, both sides of the brim (top and bottom) should be comprised on the same textile fabric. In applications where the molded hat is characterized by greater strength, it may be desirable to use a plurality of layers of textile fabric. The exact nature of the laminates prepared in accordance with this invention will be determined by the anticipated end use and the generally accepted properties of such end uses.

The fabric treatments which have been discussed above may be applied to the fabric either before or after the laminate has been prepared, although it is preferred to apply the solution prior to the formation of the laminate. Although any or all MlXTURE A by Weight Epon 812 (An aliphatic polyepoxide having an epoxide equivalent of about 179-194; available from Shell Chemical Company) Diethylene triamine Trichloroethylene MIXTURE B Epon 8l2".(An aliphatic polyepoxide having an epoxide equivalent of about 179-194; available from Shell Chemical Company) Diethylene triamine, Trichloroethylene MIXTURE C Sodium bisulfite N-methylol acetamide Textile resin FC-ZOS" (A water repellent polymeric mixture available from Minnesota Mining and Manufacturing Company) Water inu- MIXTURE D Epon 1001" (An aromatic polyepoxide available from'Shell Chemical Company and having an epoxide equivalent of about 450 to 525) Diethylene triamine Dioctyl phthalate Trichloroethylene 9 MIXTURE E Epon I001" Diethylene triamine Dioctyl phthalate Trichloroethylene 9 7 99:- \ON-AUI MIXTURE G Surlyn D-l002 (A high molecular weight interpolymer ofethylene, sodium methacrylate and methacrylic acid available from E. l. du Pont de Nemours & Co.) Water 9 MIXTURE H Diepoxide prepared from the reaction of one mole of diethylene glycol and two moles of epichlorohydrin followed by reaction with two moles of sodium hydroxide Diethylene triamine Acetic acid (glacial) Wetting agent described in Mixture F Water 7 MIXTURE l Sodium mctabisulfite l 5 N-methylol acetamide 4.9 Textile Resin FC-208 1.5 Wetting agent described in Mixture F 0 1 Water 0 MIXTURE .I

l-Iypalon 20" (A chlorosulfonated polyethylene available from E. l. du Pont de Nemours & Co.) "Adiprene L-lOO Elastomer" (A liquid 1,4-

oxybutylene glycol/toluene diisocyanate polymer of about 2000 molecular weight available from E. l. du Pont de Nemours & Co.) Trichloroethylene MIXTURE K Sodium bisulfite N-methylol methyl carbamate Ethylene glycol Diamrnonium phosphate Deceresol OT-75 Water 6 MIXTURE L Epon 1001 "Eponite 'Diethylene triamine Dioctyl phthalate Trichloroethylene 9 MIXTURE M Bisulfite addition product of 1,6- hexamethylene diisocyanate prepared by reacting 84 grams of the diisocyanate with 310 parts of a 33% aqueous solution of sodium bisulfite Wetting agent of Mixture F Urea Water 9 In carrying out the shaping operation, any suitable device or expedient may be employed. For instance, the flat composite fabric may be placed between the male and female members of a mold-like device of desired shape, either or both of which may be heated internally or externally by ordinary steam, super heated steam, steam under pressure, electrical resistance, flames and the like. Such devices may be provided with means, such as perforations or jets to supply steam to the textile fabric in order to facilitate the shaping of the composite.

While the shaping operation may be carried out in any suita-. ble device, a preferred apparatus for preparing hats is shown in FIGS. 2 to 4 wherein a frame 60 is provided with a base 61. on which is mounted an outer crown and brim mold 20 having an outer upper annular flat surface 21, an intermediate curved upper annular brim surface 22 and a crown cavity 23. Extending above the base is a pair of posts 34 having their upper ends joined together by a cross bar 36. Slidably mounted on these posts is an annular inner brim die 30 with extension rods 31, said brim die 30 having a curved inner lower annular surface 32 and the open center 33. The inner brim die 30 is mounted above the outer crown and brim mold 20 and aligned so that,

when lowered down to and against the fabric 11, the curved inner lower annular surface 32 of inner brim die 30 will be aligned with the intermediate curved upper annular surface 22 of the outer crown and brim mold 20 as shown in FIG. 3.

An inner crown die 40 is attached to support bar 42 which is slidably mounted to the posts 34 above the annular inner brim die 30 and adapted to be moved downwardly through the open center 33 of the brim die 30 contacting the fabric 1 1 moving a portion of said fabric 11 downwardly and against the sides of the cavity 23 of the outer crown and brim mold 20 as shown in FIG. 4.

While manual or mechanical means for moving the annular inner brim die 30 and inner crown die 40 downwardly into the positions shown in, FIGS. 3 and 4 may be employed, they are illustrated in FIG. 2 as an air pressure actuated means (partially shown). Two cylinders 50 are mounted to the ends of the posts 34 above the cross bar 36, said cylinders having piston rods 52 connected to the annular brim die 30 through U- brackets 53 and extension rods 31. These cylinders 50 and piston rods 52 are actuated by air pressure controlled by a manually operated valve 54, the amount of pressure being controlled by adjustable pressure valve 56. In the embodiment illustrated in FIG. 2, the downward motion of the inner crown die 40 and its support 42 which is slidably mounted to posts 34 is controlled by cylinder 44 which is mounted above the cross bar 36 and connected to support 42 by way of piston rod 46. Said cylinder 44 and piston rod 46 are actuated by air pressure (not shown), and the amount of pressure exerted by inner crown die 40 and support 42 when in the lowered position illustrated in FIG. 4 is controlled by an adjustable pressure valve (not shown). The timer 48 controls the length of time the inner crown die 40 and support 42 remains in the lowered position illustrated in FIG. 4, and automatically releases the air pressure thereby raising support 42 and inner crown die 40 at the end of the selected time.

Since heat as well as pressure is necessary to effect the desired degree of permanency to the shaped bodies, and particularly the hats prepared in the apparatus described above, heating means (not shown) are provided for heating support 42, the inner crown die 40 and the outer crown and brim mold 20. Although annular inner brim die 30 may be heated directly, the temperature of the die is raised sufficiently as a result of its contact with support 42. Generally, the die 30 is maintained in contact with heated support'42 when the apparatus is not being used.

In the normal operation of the apparatus illustrated in FIGS. 2 to 4, a piece of the fabric 1 1 approximately 20 inches square is placed above the outer crown and brim mold 20. The outer crown and brim mold 20 and inner crown die 40 and support 42 can be heated to a temperature of from l C. to about 200 C., the exact temperature being determined after considering the nature and properties of the components of fabric 1 l. The annular upper brim die 30 is lowered into the position shown in FIG. 3 by opening valve 54 which activates cylinders 50 and piston rods 52. The downward pressure exerted by brim die 30 on the composite fabric which is now in place between the brim die 30 and crown and brim mold is generally within the range of from about I to 100 p.s.i. The ideal pressure will vary depending on the fabric construction since the pressure exerted serves to control the rate and manner in which the fabric 11 is forced into the cavity 23 of outer crown brim mold 20. The use of an annular brim die with the smooth lower outer flat surface 33 which is aligned directly above the outer upper annular flat surface 21 of outer crown and brim mold 20 is preferred over other methods for applying restraining pressures to the outer edges of fabric 11 since this method results in a more uniform restraining pressure on the fabric. Other methods of restraining the fabric such as by manual restraint or other known mechanical means such as blade-type retainers or mechanically operated fingers may be utilized but are not as efficient. Uneven restraining pressure can result in stretching and thinning out of the fabric, and the formation of wrinkles which are permanently molded into the hat.

After the brim die is in position as shown in FIG. 3 and the desired pressure is applied, the heated inner crown die 40 and support 42 are lowered into the position shown in FIG. 4

by setting the timer 48 which also controls the length of time the inner crown die 40 will remain within the cavity 23. The speed at which support 42 is lowered is controlled so that the heated inner crown die will engage and progressively force the fabric 1 1 into and against the sides of heated cavity 23 to form a crown 17 of the hat body 15 as shown in FIG. 4. As the inner crown die completes its downward motion, the support 42 increases the downward pressure exerted by the inner brim die 30 and the pressure exerted on fabric 11 between elements 32 and 22 forming the brim 16 of the hat. The downward pressure exerted on the fabric by the inner crown die 40 and support 42 is generally between 20 to p.s.i., and preferably between 60 to 70 p.s.i. Generally, the apparatus is maintained in the position illustrated in FIG. 4 for a period of from about 15 seconds to 5 minutes and preferably from about 30 seconds to 3 minutes to complete the molding of the hat body 15. The preferred times will depend upon the pressure exerted, the temperature of the mold and die and the nature of the fabric. If the fabric 11 is heated for too long a period of time, the fabric may be seriously atfected resulting in the fonnation of hats which are discolored and/or stiff.

After the fabric has been subjected to the desired temperature and pressure for the selected period of time, the inner crown die 40 and support 42 and annular inner brim die 30 are raised. The molded hat body 15 is removed and has an appearance as illustrated in FIG. 1. That portion of the fabric which is maintained between flat surfaces 33 and 21 appears as the annular strip designated as element 19 in FIG. 1 while the fabric maintained between curved elements 22 and 32 during the molding operation appears as the brim 16 of the hat body. After the hat body is cooled, the crown 17 of the hat may be subjected to any desired forming operation such as can be obtained in the standard heated hat blocks. The edge of the brim 18 may then be trimmed with any suitable cutting tool, and the hat can be finished by any of the usual procedures known in the art.

The following examples illustrate the manner in which the hats of this invention may be prepared. Unless otherwise specified, all parts and percentages are by weight.

EXAMPLE 1 Several pieces (22 inches by 20 inches) of an all wool woven fabric which is 46.7 mils in thickness and weighs 7.46 ounces per square yard are treated with Mixtures A or B to a 100 percent wet pickup, dried for 5 minutes at 70 C. and cured for 5 minutes at C. Any excess of unreacted diethylene triamine is removed by gentle scouring, and the fabrics are dried in a forced-air oven at 105 C.

Mixture C is applied to some of the above-treated fabrics as well as to untreated fabrics to a 100 percent wet pickup and then dried for 30 minutes at 65 C.

Various combinations of the treated fabrics are laminated with acrylic adhesive E-358 available from Rohm & Haas and thickened with a polyester T-l2" available from National Latex and Rubber Company in the weight ratio l,000:80. The following table illustrates the various two-ply laminated fabrics prepared in this manner.

Laminate Inside Layer Outside Layer No. Treatment Treatment 1 Mixtures B and C Mixtures B and C 2 Mixtures A and C Mixtures A and C 3 Mixtures A and C Mixture C 4 Mixture C Mixture C 5 Mixture A Mixture A 6 Mixtures A and C Mixture C l-Iat shells are prepared from the above described two-ply laminates utilizing the molding apparatus described in FIGS. 2-4. In this experiment, the temperature of the inner crown die 40 and the outer crown and brim mold 20 is maintained at about C. The apparatus is operated as described previ-' ously and the inner crown die 40 is maintained in its lowered position as shown in FIG. 4 for a period of 2 minutes exerting a v EXAMPLE 2 Samples of the all wool fabric described in Example 1 (20 inches by 22 inches) are treated with Mixtures D-H to a 100 percent wet pickup, dried at 75 C. for 5 minutes and cured by heating at a temperature of 130 C. for 5 to 12 minutes. The polymer treated squares'are laminated together in pairs using natural rubber as the adhesive and then treated with Mixture l to a 100 percent wet pickup, dried at 60 C. and molded into single-unit hats as described in Example 1..The various twoply laminates treated with Mixture l and converted into hats in the manner described in Example 1 are summarized below.

Laminate Inside Layer Outside Layer No. Treatment Treatment 7 Mixture D Mixture D 8 Mixture A Mixture G 9 Mixture D None 10 Mixture E Mixture E l l Mixture F Mixture G 12 Mixture H Mixture H The hats obtained from these laminates exhibited improved shape retention and recoverability properties.

EXAMPLE 3 A molded hat is prepared from a laminate obtained from two 20 inch squaresof the all wool fabric described in Example 1 by padding two layers of the fabric to a 100 percent wet pickup with Mixture J, pressing the two layers together and allowing the laminate to dry. A molded hat prepared from this laminate in accordance with the procedure described in Example 1 exhibits good shape retention, resilience and flexibility.

EXAMPLE 4 A polymeric:coating composition is prepared as follows: Into a jacketed stainless steel reactor is poured 225 pounds of polypropylene. glycol adduct of glycerin having a molecular weight of about 5,000. The reactor is then closed and the pressure therein reduced to about 10 mm. mercury after which the reactor is flushed with dry nitrogen. After the pressure regulation and flushing operation is repeated for 3 cycles, 23 pounds of dry toluene is poured into the reactor. A blanket of nitrogen gas ismaintained in the vessel throughout the reaction. The pressure is again reducedto 10 mm. mercury and the reactor is heated to 140 C. to distill off the toluene, after which it is cooled to room temperature using cold water in the jacket around the reactor. The pressure is returned to normal, and after stirring for 15 minutes to thoroughly mix the components, about twice the stoichiometric quantity for reaction with the glycol of tolylene-2,4-diisocyanate is added rapidly and stirred until the heat of reaction ceases andthe temperature has risen slowly up to 40'45 C. The temperature of the reaction mixture is then raised at the rate of about 2 C. per minute to a temperature of 146 C. where it is held for 18 minutes; thereafter, the mixture is cooled at a rate of about 2 C. per minute to a temperature of 100 F. Sufficient trichloroethylene is added to provide a solution containing 70 percent of the resulting pre-polymer. The pre-polymer solution is then transferred from the reactor to a pre-dried drum under a dry nitrogen atmosphere to avoid water contamination. At the time of the transfer, the pre-polymer solution has a color of from colorless to a very pale straw color.

Samples of an all wool fabric as described in Example 1 are padded to a 100 percent wet pickup with a trichloroethylene solution containing 25 percent of the pre-polymer composition prepared above and 3 percent Quadrol (N,N', N-

tetrakis-2-hydroxypropyl ethylenediamine marketed by Wyandotte Chemical Corporation), dried for 5 minutes at 70 C. and cured for 7 minutes at C.

A laminate was prepared by spraying two layers of the treated fabric with a methylene chloride solution containing 20 percent Urethane Adhesive 200 and 3 percent zinc naphthenate, and thereafter pressing the layers together allowing the solvent to evaporate. A hat shell prepared in accordance with the procedures described in Example 1 is free of wrinkles and exhibits shape retention and recoverability properties.

EXAMPLE 5 Samples of the all wool fabric described in Example 1 are padded to a 100 percent wet pickup with a trichloroethylene solution containing 5 percent of Zeset TP, a terpolymer of ethylene, vinyl acetate and methacryloyl chloride having a molecular weight of about 50,000 and available from'E. l. du Pont de Nemours & Co. The treated fabric is dried at 38C., and a two-ply laminate is prepared using the adhesive described in Example 4. A hat shell prepared from this two-ply laminate in accordance with the procedure described in Example l exhibits excellent shape retention and recoverability properties.

EXAMPLE 6 Samples of the all wool fabric described in Example 1 are padded with Zeset T? to provide a 3 percent dry pickup on the fabric. These treated samples are then padded to a 70 percent wet pickup with Mixture K and dried at 75 C. Two-ply laminates are prepared using a Neoprene adhesive, and the laminates are converted to hat shells according to the procedure described in Example 1.

EXAMPLE 7 The procedure of Example 6 is repeated except that the wool fabric is replaced with a wool: rayon blend containing 50 percent rayon.

EXAMPLE 8 Samples of acrilan/wool fabric (55:45) are padded to 100 percent wet pickup with Mixture G or L, dried at 75 C. and cured at C. Those fabrics treated with Mixture L are delicately washed for 4 minutes to remove excess amine and then dried. Two ply laminates were prepared by bonding one layer of fabric treated with Mixture G and one layer of fabric treated with Mixture L with a natural rubber adhesive. Hat shells are prepared so that the outside layer is a fabric treated with Mixture G according to the procedure described in Example 1 except that the downward pressure exerted by the annular brim die is 40 pounds per square inch and the downward pressure exerted by the inner crown die is 80 pounds per square inch. The hat shells were molded on a conventional blocking mold at C. for 3 minutes and exhibited the usual desirable properties.

EXAMPLE 9 laminate utilizing Urethane 200 containing zinc naphthenate catalyst as the adhesive.

EXAMPLE 10 The procedure of Example 2 is repeated except that the all wool fabric is a felted fabric prepared by washing the woolen fabric 5 times with detergent at 60 C. The felt like hat obtained in this manner exhibits the desired properties of shape retention and resilience.

EXAMPLE 11 EXAMPLE 12 The procedure of Example 1 is repeated except that the hat shell is prepared from a single layer of the treated wool fabric.

EXAMPLE l3 Samples of the all woolen fabric described in Example 1 are padded to a l percent wet pickup with Mixture M and airdried. A two-ply laminate is prepared from two layers of the treated fabric bonded together with a natural rubber adhesive. The laminate is converted to a hat shell in accordance with the procedure described in Example 1, and the hat shell obtained in this manner exhibits the desirable properties of shape retention and resilience.

EXAMPLE 14 The all wool fabric described in Example 1 is impregnated with a sulfuric acid solution (1N) containing ferrous ammonium sulfate to provide the fabric with 0.2 percent of the weight of the fabric of ferrous ammonium sulfate. This fabric is then introduced into an aqueous solution containing 5 percent methacrylic acid and 0.02 parts per liter of hydrogen peroxide (30 percent). A 25 percent wet pickup (by weight) was obtained. After drying the treated fabric, two layers were bonded together with Urethane 200 TCE adhesive and a hat shell was prepared in accordance with the procedure of Example 1.

EXAMPLE A piece of an all wool fabric as described in Example 1 is padded to a 100 percent wet pickup with an aqueous solution containing 12 percent acrylamide and 0.1 percent of a nonionic wetting agent obtained by condensating nonyl phenol with ethylene oxide in a molar ratio of 19.5. The wool is then dried for ID minutes at 95 C. and allowed to stand at room temperature for 4 hours.

The dried fabric is then subjected to irradiation in an insulated core transformer manufactured by High Voltage Engineering Corporation of Burlington, Mass. The fabric is passed through the irradiation equipment at a rate of 40 yards per minute at a setting on the transformer of 500 kilovolts and 15 milliamps to produce a dosage of 2 megarads. A two-ply laminate is prepared from this treated fabric using a natural rubber adhesive and converted into a hat shell in the apparatus described in Example 1 at a temperature of 163 C., under a pressure of 10 pounds per square inch for 2 minutes and 20 seconds.

EXAMPLE 16 v The procedure of Example l5 is repeated except that the two-ply laminate is prepared prior to the irradiation.

As can be seen from the above description and Examples this invention provides a method for preparing hats having unusual shape retention qualities. The hats are further characterized by improved shape definition and resistance to stress release and puckering. For example, the hats obtained from this invention which are deformed, either by crushing or twisting, wet with water or dry-cleaned by conventional methods will return to and maintain their molded shape without the necessity of subsequent refinishing. Furthermore, since the hats are prepared under conditions which do not adversely affect the nature and characteristics of the textile fabric utilized, normal and unusual efiects can be produced by the selection of particular patterns of fabrics.

What is claimed is:

l. A hat having improved shape retention and recoverability pro rties including as a rinci al component thereof a mo ded woven, knitted or braided abric forming a crown portion and a surrounding brim portion, said fabric including at least about 20 percent keratin fibers which have been stabilized prior to molding by reaction with a polymeric composition selected from the class consisting of reactive copolymers and terpolymers based on vinyl type monomers, reactive polyurethanes, and reactive polyolefins; said polymeric composition comprising between about 2 and 20 percent by weight of said fabric.

2. The molded hat of claim 1 wherein the fabric of the crown and brim is a laminated fabric.

3. The molded hat of claim 1 wherein the stabilizing polymeric composition is a reactive polyethylene composition. 

1. A hat having improved shape retention and recoverability properties including as a principal component thereof a molded woven, knitted or braided fabric forming a crown portion and a surrounding brim portion, said fabric including at least about 20 percent keratin fibers which have been stabilized prior to molding by reaction with a polymeric composition selected from the class consisting of reactive copolymers and terpolymers based on vinyl type monomers, reactive polyurethanes, and reactive polyolefins; said polymeric composition comprising between about 2 and 20 percent by weight of said fabric.
 2. The molded hat of claim 1 wherein the fabric of the crown and brim is a laminated fabric.
 3. The molded hat of claim 1 wherein the stabilizing polymeric composition is a reactive polyethylene composition. 